Materials and Corrosion 2014, XXX, No.

XXX

DOI: 10.1002/maco.201307448

Corrosion behavior of X65 carbon steel in simulated oileld produced water

Y. L. Zhang, M. Du*, J. Zhang and J. Q. Du
Corrosion behavior of X65 steel in simulated oileld water was studied by weight loss, polarization curve, electrochemical impedance spectroscopy, scanning electron microscope, and Xray diffraction methods. Effects of temperature, acetic acid concentration, and CO2 partial pressure on the corrosion behavior were discussed. Results showed that the corrosion rate increased with the increasing of temperature, acetic acid concentration, and CO2 partial pressure. High temperature favored the formation of FeCO3; the addition of acetic acid could speed hydrogen depolarization, but the more acetic acid could remove FeCO3 layer, CO2 mainly inuenced the cathodic reaction, appearing limiting diffusive current density. Acetic acid and CO2 had a synergistic effect on the corrosion process of X65 carbon steel in simulated oileld produced water.

1 Introduction
Amounts of oileld produced water were produced in the process of the oil and gas eld. In recent years much high salinity, CO2, acetic acid, and H2S have been found, so that the corrosion rate was enhanced in the oileld produced water. Carbon steels are extensively used in oil industries, in which X65 carbon steel is one of the most common materials used as tubing. However, carbon steels are susceptible to corrosion in environment containing oileld produced water. Therefore, the corrosion of carbon steel in oileld produced water has become an important issue. Lots of researchers showed that raising temperature could accelerate chemical reactions, electrochemical reaction, and mass transfer process. So it could accelerate occurrence to corrosion [1 6]. Zhu et al. [7] proposed that increasing temperature not only enhanced the dissolution of steel substrate, but also promoted the precipitation of FeCO3 protective scale. Honarvar Nazari et al. [8] studied the inuence of temperature on the corrosion products. They showed that the threshold temperature for forming iron carbonate layer was 65 8C, below which no carbonate was detected. With increasing temperature, the apparent density and thickness of FeCO3 scale were improved. Acetic acid was commonly found in oil, the presence of acetic acid has an important impact on the corrosion reaction [912]. It has been accepted that undissociated acetic acid is critical for corrosion of steel. Garsany et al. [13] suggested that acetic acid

would act as a reactant in the cathodic process, which could enhance greatly the cathodic reaction rate in oileld conditions. However, George et al. [14] proposed that acetic acid actually acts as a weak inhibitor for anodic dissolution reaction of steel. It is not due to any inuence of acetic acid on the cathode reduction of H or on the anodic dissolution of steel, but due to its effect on the protectiveness of the formed corrosion scale layer. It has been acknowledged that CO2 corrosion is one of the major corrosion types resulting in oil well failure [15]. Carbon dioxide gas hydrates in water and changes to carbonic acid, which causes the intensive corrosion in oil eld. The reactions are responsible for CO2 corrosion. Chemical reactions are [16]:

CO2 g ! CO2 aq CO2 aq H2 O ! H2 CO3

Then carbonic acid dissociates as below [16]:

1 2

H2 CO3 ! H HCO 3
2 HCO 3 ! H CO3

3 4

Y. L. Zhang, M. Du, J. Zhang, J. Q. Du Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, 238 Songling Road, Qing dao 266100, (P. R. China) E-mail: ssdm99@ouc.edu.cn

In the presence of acetic acids, the corrosive media in the solution would be enhanced dramatically in CO2 corrosion [13 17]. Zhu et al. [7] indicated that the corrosion process in CO2 containing water with the presence of acetic acid was complicated. With increasing of acetic acid concentration, the corrosion process could be controlled by H2CO3, HAC, and H2 CO 3 HAC mixed. Liu et al. [18] investigated the effect of acetic acid using electrochemical impedance spectroscopy (EIS) method. They

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found that the surface chemical reactions of cathodic reduction were enhanced in the presence of acetic acid. They also found that acetic acid can remove FeCO3 layer. Zhang and Cheng [13] reported similar results. In addition, they observed an increase in the current density of anodic reactions and they saw localized corrosion on the surface of steel. To date, there has been limited work on the corrosion of X65 carbon steel tubing in oileld produced water include acetic acid and CO2 under high temperature and high pressure. In this work, the corrosion behavior of X65 carbon steel in oileld produced water was investigated by weight loss test, electrochemical measurements, scanning electron microscopy (SEM), and Xray diffraction (XRD) methods. Effects of temperature, acetic acid concentration, and CO2 partial pressure on the corrosion process of X65 carbon steel were discussed in terms of corrosion rate and then explored in depth the corrosion mechanism. It is expected that this study would provide the foundation for appropriate corrosion protection in the future.

Rmass

m0 m1 S 0t

g=m2 h

Vp

Rmass 24 365 Rmass 8:76 r r 1000

mm=a

where m0 and m1 are the original weight and nal weight of specimens, respectively, g; S0 is the exposed surface area of specimens, m2; t represents the immersion time, h; and r is the steel density, 7.86 g/cm3. 2.2 Electrochemical measurement Electrochemical measurements were performed with a three electrode cell through a Zahner IM6e (Germany) electrochemical measurement system. The working electrode was in the form of a square form (10 10 3 mm3) X65 steel embedded in PVC holder using epoxy resin with exposed working area of 1 cm2. A platinum electrode and an Ag/AgCl electrode were used as auxiliary and reference electrodes, respectively. Prior to electrochemical measurements, the electrode was immersed in the test solution for 0.5 h until steadystate corrosion potential was reached. The experiments were repeated for many times to ensure reproducibility. Electrochemical impedance spectroscopy (EIS) was measured with an application of 10 mV amplitude sinusoidal voltage as disturbance signal, in a frequency range from 100 kHz to 10 mHz at OCP. The results of EIS measurements were analyzed by using the Zview software. Potentiodynamic polarization tests were carried out after EIS measurements. The polarization curves were performed at a potential range from 0.3 to 0.5 V versus OCP with a scan rate of 1 mV/s, scanning from the cathodic to the anodic direction. All tests were performed at 20 and 90 8C, respectively. The basic test solution was simulated oileld produced water with various concentrations of acetic acid and CO2. 2.3 Surface analysis The surface morphology was characterized by a JSM6700F (Japan) scanning electron microscope (SEM) and corrosion products structure was analyzed by D8ADVANCE (Germany) Xray diffraction (XRD).

2 Experimental
2.1 Material and solution X65 steel was used for this study, its composition (wt%) was 0.08% C, 0.30% Si, 1.17% Mn, 0.004% S, 0.026% P, 0.009% Nb, 0.009% Mo, and balanced Fe. The simulated oileld produced water was prepared by analytical grade reagents and deionized water, which pH is 7.98. The chemical composition is shown in Table 1. Weight loss tests were conducted in ZCF2L autoclave to investigate corrosion rate of X65 carbon steel. The test specimens were machined to a size of 3 10 100 mm3. Tests were carried out in an autoclave at total pressure 0.5 MPa for 72 h. The detailed test conditions of weight loss tests are as follows: ve temperatures of 20, 40, 60, 80, and 90 8C (controlling CHAc 1000 ppm and P CO2 0.1 MPa) and ve CHAc of 0, 500, 1000, 1500, and 2000 ppm (controlled temperature 60 8C and P CO2 0.1 MPa) and P CO2 of 0, 0.05, 0.1, 0.15, and 0.2 MPa (controlled temperature 60 8C and CHAC 1000 ppm). Three equivalent specimens were used for each test condition in order to ensure the reproducibility. Prior to tests, High purity nitrogen was introduced into the autoclave to remove oxygen. The specimens were cleaned with distilled water and acetone, dried, and then weighed using FA2004Ndigit electronic balance with a precision of 1/10 000 before weight loss test. After completion of tests, the corroded specimens were rinsed with distilled water. The corrosion products were removed according to GB/T165451996, and then rinsed and dried again. The corrosion rate Vp (mm/a) was reported by the following formula:

3 Results and discussion

3.1 Weight loss test Figure 1 shows the values of corrosion rate obtained from weight loss test as the function of temperature, acetic acid concentration,

Table 1. Chemical composition of produced water extracted from oileld (mg/L)

Composition
Content (mg/L)

NaCl
16.6172

KCl
0.3553

MgCl2
1.6603

CaCl2
0.5053

Na2SO4
1.1096

NaHCO3
3.0638

Na2CO3
0.0322

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Materials and Corrosion 2014, XXX, No. XXX

Corrosion behavior of X65 carbon steel

3.0 2.5 2.0

high temperature and high CO2 partial pressure, especially with high acetic acid concentration, is a great threat to the safety of oil industry. 3.2 Electrochemical analysis 3.2.1 Polarization curve measurements The potentiodynamic experiments were performed with a proper potential range and scan, and some key characteristics of the anodic and cathodic kinetics appeared useful to handle our case. In Fig. 2 selected polarization curves from 20 to 90 8C conditions are shown. Electrochemical corrosion kinetics parameters such as corrosion potential (Ecorr), anodic and cathodic Tafel slopes (ba, bc) and corrosion current density (Icorr) were listed in Table 2. It shows that the presence of acetic acid or CO2 caused a prominent increase in the corrosion current density (Icorr). The corrosion potential shifted towards to the positive direction from 0.80 V at 20 8C changing to 0.78 V at 90 8C as shown in Table 2, apparently. With the increasing of temperature, the anodic Tafel slopes ba and the cathodic Tafel slopes bc changed a lot, which indicated that the high temperature modied the mechanism of the reactions of hydrogen evolution on the negative electrode and anode dissolution. According to the

Vp, mm/a

1.5 1.0 0.5

0.0 10 20 30 40 50 60 70 80 90 100

T
2.5 2.0

Vp, mm/a

1.5 1.0 0.5

b
0.0 0 500 1000 1500 2000

-1 -2

CHAc, ppm
-2
4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0.00 0.05

blank HAc 2000ppm CO2-saturated mix

-3 -4 -5 -6 -7

LogI/A.cm

Vp, mm/a

-1.0
c

-0.8

-0.6

-0.4

-0.2

Potential /V(vs.Ag/AgCl)
0.10 0.15 0.20

-1 -2 LogI/A,cm -3 -4 -5 -6 -7 -2

PCO , Mpa
2

blank HAc 2000ppm CO2-saturated mix

Figure 1. Corrosion rate of X65 carbon steel with different conditions: (a) temperature, (b) acetic acid concentration, and (c) CO2 partial pressure in oileld produced water

and CO2 partial pressure in simulated oileld produced water, respectively. The average corrosion rate was used in the work. It has been observed that the corrosion rate of X65 carbon steel increased with the increasing of temperature, acetic acid concentration, and CO2 partial pressure. The corrosion rate was estimated to be the highest at 90 8C, CO2 partial pressure 0.2 MPa and the concentration of 2000 ppm acetic acid in simulated oileld produced water. With regard to the corrosion rate under

-1.0

-0.8 -0.6 -0.4 -0.2 Potential /V(vs,Ag/AgCl)

Figure 2. Polarization curves of X65 carbon steel at different conditions: (a) 20 8C and (b) 90 8C of oileld produced water

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Table 2. Results of polarization curve tting at different conditions in oileld produced water

T ( 8C) 20

CHAc/ppm 0 2000 0 2000 0 2000 0 2000

C CO2 Noaddition Noaddition Saturation Saturation Noaddition Noaddition Saturation Saturation

Ecorr (V vs. Ag/AgCl) 0.80 0.77 0.73 0.69 0.78 0.76 0.74 0.70

ba (mV/dec) 150 90 200 68 51 97 111 279

bc (mV/dec) 169 189 270 817 225 262 310 268

Icorr (A/cm2) 1.09 3.92 84.7 207 40.5 122 374 597

90

polarization curves at 20 and 90 8C as shown in Fig. 2, temperature has little inuence on the anodic reaction, it is concluded that the corrosion is mainly dominated by cathode reaction in blank oileld produced water. The addition of 2000 ppm acetic acid in oileld produced water had shifted the corrosion potential about 30 mV to positive, the anodic active dissolution was intensied at 20 8C. The corrosion potential increased about 10 mV at 2000 ppm acetic acid, 90 8C compared to 2000 ppm acetic acid, 20 8C. This reaction could be the reduction of the acetic acid [7,10]:

cathodic reactions, which could be attributed to the additional reduction of acetic acid [21,22].

CO2 H2 O Ac ! HCO 3 HAc

12

HAc e ! 1=2H2 AC

Thus CO2 and acetic acid played a synergistic effect on the corrosion reaction, similar results have been reported in previous work [22]. It can be clearly seen that the corrosion current density increases with increasing temperature, with the increase of concentration of acetic acid, and with the increase of CO2 concentration, as illustrated in Table 2, which was consistent with

At the same time there was a high corrosion rate at 90 8C with 2000 ppm acetic acid as shown in Table 2. This is because the higher temperature promoted the acetic acid to ionize more H, lowering solution pH, and hydrogen depolarization process would become easy, so the corrosion rate is accelerated. With the addition of saturated CO2 at the same temperature, the anodic current density and the cathodic current density increased, rapidly, compared to the blank. When temperature was raised from 20 to 90 8C, the corrosion current density increased from 84.7 to 374 A/cm2. Reducing ion HCO 3 increased due to the increased concentration of CO2 in solution, so depolarization was enhanced. Under this condition CO2 is the main inuencing factor of cathodic reaction on the corrosion process. The predominant cathodic reaction was the reduction of bicarbonate ion as shown below [19,20]:

6000 5000

300 200 100 0 0 100 200 300

-ZIm/.cm2

4000 3000 2000 1000 0

blank HAc 2000ppm CO2-saturated mix

1000 2000 3000 4000 5000 6000 2 ZRecm

CO2 g ! CO2 aq CO2 H2 O ! H2 CO3 H2 CO3 ! H HCO 3 2HCO 3 2e ! H2

2CO2 3

8 9 10 11

700 600 500 400 300 200 100 0 0

150 100 50 0 0 50 100 150

blank HAc 2000ppm CO2-saturated mix

There was limiting diffusive current density in the cathodic curve with the addition of 2000 ppm acetic acid in CO2saturated oileld produced water (Fig. 2). The polarization behavior at 90 8C was similar to that at 20 8C. It is acknowledged that the addition of acetic acid is able to accelerate the anodic reactions and the
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100 200 300 400 500 600 700 2 ZRe/cm

Figure 3. Nyquist diagrams of X65 steel at different conditions: (a) 20 8C and (b) 90 8C of oileld produced water

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Materials and Corrosion 2014, XXX, No. XXX

Corrosion behavior of X65 carbon steel

4.5 4.0
2

3.5 3.0 2.5 2.0 1.5 1.0 0.5 -3 -2

90 blank HAc 2000ppm 80 CO2-saturated 70

mix

-1 0 1 2 3 Log Frequency/Hz

60 50 40 30 a 20 10 0 4 5

4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 -3 -2 -1

Log|Z|/.cm

mix

Phase/Degree

90 blank HAc 2000ppm 80 CO2-saturated 70 60 50 40 30 20 10 0

Phase/Degree

Log|Z|/cm

0 1 2 3 4 Log Frequency/Hz

Figure 5. Electrochemical equivalent circuits for tting the experimental impedance data at different conditions of oileld produced water: Rs, solution resistance; CPE, constant phase element; Rct, chargetransfer resistance; R1, inductance resistance; L1, inductance; R2, resistance of corrosion product lm

Figure 4. Bode plots of X65 steel at different conditions: (a) 20 8C and (b) 90 8C of oileld produced water

the weight loss results. There is the maximum corrosion rate at the mixing conditions. 3.2.2 EIS measurements Some EIS tests were performed to study the acetic acid and CO2 effect on the double layer and charge transfer, and to nd any consistency with the polarization results. The Nyquist plots and Bode diagrams of X65 steel were shown at their respective OCP under static condition in Figs. 3 and 4. The impedance parameters obtained by circuit tting were listed in Table 3. Chargetransfer resistance Rct is usually used to evaluate the corrosion resistance of the electrode. The higher Rct shows the greater resistance to metal ionization process, which indicates the better corrosion resistance of metallic materials. It is clear

that there was a time constant existing in the EIS curve at 20 8C in blank solution (Fig. 3a). The impedance diagrams obtained are not perfect semicircles, and this difference has been attributed to frequency dispersion. That was a capacitive semicircle. This corresponds to a peak in the phase angle plots from Fig. 4a. An electrochemical equivalent circuit, as shown in Fig. 5a, was used to t the measured impedance data. Figure 3b shows a capacitive semicircle in the high frequency range and a capacitive semicircle in the low frequency range at 90 8C in blank solution (Fig. 3b), and the low frequency capacitive loop indicated that the X65 steel surface was partially covered with corrosion scale. The electrochemical equivalent circuit was shown in Fig. 5c. The diameter of the capacitive loop decreased with increasing temperature. With the addition of 2000 ppm acetic acid, the capacitive, relatively overlapped Nyquist spectra, shown in Fig. 3a at 20 8C, suggested the interactions were mainly governed by adsorption.

Table 3. Electrochemical impedance parameters tted from the measured EIS data at different conditions in oileld produced water

T ( 8C) CHAc (ppm) 20 0 2000 0 2000 0 2000 0 2000

C CO2 Noaddition Noaddition Saturation Saturation Noaddition Noadding Saturation Saturation

Rs (V cm2) (CPE)1 (mF/cm2(n1)) Rct (V cm2) (CPE)2 (mF/cm2(n2)) R2 (V cm2) L1 (H/cm2) 6.288 5.214 4.743 4.785 3.226 2.507 2.7111 2.582 0.21 0.29 0.32 0.68 0.58 0.60 0.75 1.17 (0.76) (0.73) (0.76) (0.75) (0.78) (0.73) (0.73) (0.85) 5678 1270 291 114 525 123 89 33 0.0148 (0.67) 0.0335 (0.96) 0.0212 (0.66) 0.258 (0.95) 221 29 61 7 805 215

90

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We believe adsorption was sustained by iron intermediates originated from multistep dissolution. However, we could see that the diameter of the capacitive loop and modulus values were obviously reduced compared to blank solution. The peak of phase angle also decreased at 2000 ppm acetic acid, 20 8C (Fig. 3a). The electrochemical equivalent circuit was shown in Fig. 5a. However, the Nyquist diagrams contained two capacitive semicircles over the whole frequency range at 2000 ppm acetic acid, 90 8C, which corresponded to two time constants in Bode plot (Fig. 4b). The electrochemical equivalent circuit was shown in Fig. 5c. It can be seen that, the impedance spectra exhibited a capacitive semicircle in the high frequency range and an inductive loop in the low frequency range in CO2saturated solution at 20 8C from Fig. 3a. The inductive loop is usually related to adsorb the intermediate product of the corrosion reaction [23,24]. The electrochemical equivalent circuit was shown in Fig. 5b. Electrode surface is completely covered with corrosion products due to intensify corrosion reaction in CO2 saturated solution at 90 8C, which showed lowfrequency inductive loop to disappear [4,5]. It was seen that there were two capacitive semicircles from Fig. 3b at CO2saturated solution. The electrochemical equivalent circuit was shown in Fig. 5c. There was similar characteristic to EIS diagrams between CO2 saturated solution without acetic acid and with 2000 ppm acetic acid (Fig. 3), but the diameter of the semicircle decreased, which indicated that the corrosion rate of X65 carbon steel increased. It could be only seen that there was a decrease of the impedance values in the presence of 2000 ppm acetic acid of CO2saturated solution, The high and low frequency loops are attributed to the chargetransfer resistance of the corrosion reactions occurring at the solution/layer and layer/steel interface, respectively. The shrinkage in them showed an increase in corrosion rate. The tting results showed that the Rct values decreased and the Cd values increased with the addition of acetic acid or CO2 in simulated oileld produced water, indicating that the corrosion rate increased. The general behavior of EIS was, however, in good agreement with previous results from the recent literature [7]. The polarization curve and electrochemical impedance spectroscopy were measured to CO2saturated solution with 2000 ppm acetic acid at 20 and 90 8C for 48 h. The polarization curve at different immersing time in mix solution is shown in

500 400

120 80 40 0 0 40 80 120

-ZIm/.cm2

300 200 100 0

20mix0h 90mix0h 20mix48h 90mix48h

100

200 300 400 2 ZRe/cm

500

4.0 3.5 3.0

2

2.0 1.5 1.0 0.5 0.0 -3 -2 -1 0 1 2 3 Log Frequency/Hz 4

Figure 7. Nyquist diagrams (a) and Bode plots (b) of X65 steel for different time

-1 -2
-2

LogI/A.cm

-3 -4 -5 -6 -7 -1.0

20mix0h 90mix0h 20mix48h 90mix48h

Fig. 6. Figure 7 shows the Nyquist diagrams and Bode plots measured on X65 steel in mix conditions. It is seen that the corrosion potential shifted 10 mV towards the negative direction when the samples were immersed in the mix solution for 48 h at 20 8C. The more negative the corrosion potential, the easier the corrosion occurs [6]. The cathode reaction was suppressed due to the existence of corrosion product. There was a higher corrosion current density compared to the early immersion as shown in Table 4. It is obvious that there was a major increase in the corrosion rate. By increasing to 90 8C at 48 h, a big shift in the corrosion potential of about 70 mV to more positive potentials was observed. There was no limiting diffusive current density in the cathodic curve and the steel was in inactive dissolution status (Fig. 6). The corrosion current density signicantly decreased (Table 4) due to the formation of protective iron carbonate in the surface of the electrode (Table 5). Rct and Rf increased with increasing time at 90 8C.
Table 4. Results of polarization curve tting at different immersing time in mix solution

T ( 8C)

t (h) 0 48 0 48

Ecorr (V vs. Ag/AgCl) 0.69 0.70 0.70 0.79

ba (mV/dec) 68 279 214 63

bc (mV/dec) 817 268 439 153

Icorr (A/cm2) 207 168 597 66.5

-0.8 -0.6 -0.4 -0.2 Potential /V(vs.Ag/AgCl)

20 90

Figure 6. Polarization curves of X65 steel at different immersing time in mix solution

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Phase/Degree

Log|Z|/cm

2.5

20mix0h 90mix0h 20mix48h 90mix48h

90 80 70 60 50 40 b 30 20 10 0

Materials and Corrosion 2014, XXX, No. XXX

Corrosion behavior of X65 carbon steel

Table 5. Electrochemical impedance parameters tted from the measured EIS data at different immersing time in mix solution

T ( 8C) 20 90

t (h) 0 48 0 48

Rs (V cm2) 8.792 14.209 3.311 1.911

(CPE)1 (mF/cm2(n1)) 0.68 4.49 1.17 0.406 (0.75) (0.90) (0.85) (0.82)

Rct (V cm2) 114 95 33 154

(CPE)2 (F/cm2(n2)) 0.258(0.95) 0.0083(0.95)

R2/Rf (V cm2) 7 368

Lw (H/cm2) 215 852

The Nyquist plots and Bode plots obtained for the samples were shown in Fig. 7. Sample for 0.5 h exhibited a capacitive semicircle in high frequency region followed by an inductive loop in low frequency region at 20 8C which could be attributed to the formation of corrosion products on the surface of steel. After 48 h of immersion, the capacitive semicircle decreased and the inductive loop shrank (Fig. 7a). An electrochemical equivalent circuit was shown in Fig. 8a. On the other hand, after 48 h of immersion at 90 8C, the Nyquist plot exhibited a very large capacitive semicircle in the high frequency range, Rct increased as shown in Bode plots (Fig. 7b). Such changes were attributed to the formation of a protective scale. Figure 8b indicated the electrochemical equivalent circuit for X65 steel immersed 48 h at 90 8C. 3.3 Surface analysis
Figure 8. Electrochemical equivalent circuits for tting the experimental impedance data at different immersing time: (a) 20 8C and (b) 90 8C: Rs solution resistance; CPE, constant phase element; Rct, chargetransfer resistance; R1, inductance resistance; L1, inductance; Rf, resistance of corrosion product lm

Surface analysis has been carried out to further understand the surface properties and morphology and their effects on electrochemical corrosion behavior. SEM micrographs of the specimen at 20 8C were given in Fig. 9, which showed that there was little corrosion product lm

Figure 9. SEM micrographs of the specimens at 20 8C: (a) blank; (b) 2000 ppm HAc; (c) saturated CO2; and (d) mix with oileld produced water for 72 h

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Materials and Corrosion 2014, XXX, No. XXX

Fe

Fe FeCO3 Fe

intensity

mix
saturated CO2 2000ppm HAc

intensity/cps
70 80

Fe

mix

saturated CO2

2000ppm HAc blank

blank
10 20 30 40 50 60 2-Thetadegree

10

20

30 40 50 60 2-Thetadegree

70

80

Figure 10. XRD patterns of the specimens at 20 8C under oileld produced water for 72 h

Figure 12. XRD patterns of the specimens at 90 8C under oileld produced water for 72 h

formed on the surface of steel; The XRD patterns of the samples were shown in Fig. 10. There was the only observed peak associated with iron (Fe). Both indicated that the lower temperature is not conducive to the formation of corrosion products. The surface morphologies and XRD spectra on the corroded specimens at 90 8C for various conditions are shown in Figs. 11 and 12, respectively. It can be seen from Fig. 11a and c, that square crystal shape was formed on the surface of X65 steel, but there were few corrosion product in Fig. 11b. At the same time the peaks associated with iron carbonate and iron can be seen in Fig. 12 at

blank and saturatedCO2 specimens. The expert [7] pointed out the acetic acid was able to dissolve corrosion product FeCO3.

FeCO3 2HAc ! Fe2 2AC H2 CO3

13

The dissolution and formation of FeCO3 on steel surface in CO2 containing solution with 2000 ppm acetic acid can be expressed as follows:

FeCO3 2HAc ! Fe2 2AC H2 CO3

14

Figure 11. SEM micrographs of the specimens at 90 8C: (a) blank; (b) 2000 ppm HAc; (c) saturated CO2; and (d) mix with oileld produced water for 72 h

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Materials and Corrosion 2014, XXX, No. XXX

Corrosion behavior of X65 carbon steel

Fe2 H2 CO3 ! FeCO3 2H Fe H2 CO3 ! FeCO3 H2

15 16

Therefore, the formation of FeCO3 is a dynamic process with the addition of acetic acid. It is understood that mainly iron carbonate lm can block the surface of steel as a protective scale [8,2527]. The corrosion product layer, as shown in Fig. 10d was completely compact, and it has a very good protection effect on the X65 steel surface, which decreased the corrosion rate. This is in good agreement with SEM and polarization results.

4 Conclusions
1. Uniform corrosion is the main behavior to X65 carbon steel in the simulated oileld produced water. 2. The corrosion rate increased with the increase of temperature from 20 to 90 8C. Temperature played a signicant role in the formation of corrosion products. The surface of X65 steel formed FeCO3 at 90 8C. 3. Corrosion rate of X65 carbon steel increased with acetic acid concentration among 02000 ppm. Acetic acid can accelerate anode corrosion at low temperature; however the high temperature can promote the acetic acid to ionize, thus speeding hydrogen depolarization. The acetic acid could remove FeCO3 layer. 4. The corrosion rate of X65 steel linearly increased with the partial pressure of CO2. CO2 has the main inuence on cathode reaction, appearing limiting diffusive current density. The addition of acetic acid has a synergetic effect in CO2 saturated solution. There was the maximum corrosion rate at the mix conditions.

5 References
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